TWI576381B - Chloroprene rubber foaming material and manufacturing method of rubber composite layer using the same - Google Patents

Description

Neoprene foaming material and method for producing rubber composite layer using the same

The present invention relates to a neoprene foamed material and product, and more particularly to a method for producing a neoprene foamed material suitable for foaming and vulcanization in an open system and a rubber composite layer using the foamed material.

Neoprene (CR) is a common foaming polymer material. Besides the good physical properties of general foamed rubber, it also has excellent properties such as weather resistance, flame resistance, oil resistance and chemical resistance. It is widely used in household appliances and automobiles. Packaging, shipping and other industries.

In the past, neoprene foam products were made by using a closed system, that is, using a mold to foam and vulcanize the rubber under a pressure and solid heat source. However, the products produced by the closed system are discontinuous, the production process is intermittent, the production time is relatively long, and the energy consumption is high.

In addition, the use of an open system means that the hot air is used as a medium for conducting heat in the oven to foam and vulcanize the rubber. However, due to the vulcanization characteristics of the neoprene itself, the foaming pores are large and the vulcanization curve is slow; if the vulcanization rate is too slow, meaning that the scorch time is too long, the colloid cannot enclose the gas generated by the blowing agent, and the production Efficiency also decreases.

Therefore, it has become an important issue for a neoprene foamed material with a slow vulcanization curve to be vulcanized with a foaming agent without a mold pressure and at a vulcanization temperature of 140 to 150 ° C in an open system. In view of this, the applicant of the present invention specially developed a method for manufacturing a neoprene foamed material and a rubber composite layer using the same, which can be used for foaming of an open system for foaming. And vulcanization, at the same time can produce rubber products in a short time, suitable for batch and continuous process production, enough to overcome the various problems mentioned above.

In view of the above problems, the present invention is directed to the absence of the prior art, and its main object is to provide a method for manufacturing a neoprene foamed material and a rubber composite layer using the same, through a specially designed neoprene foaming formulation. It can successfully overcome the vulcanization characteristics of neoprene itself, can greatly shorten the scorch time, and achieve low-density continuous production of neoprene foam materials and products, and promote the improvement of production efficiency.

Another object of the present invention is to provide a chloroprene rubber foaming material and a method for producing the rubber composite layer using the foaming material, which can meet the environmental protection standard, does not generate formaldehyde gas during foaming, and can be used together with low temperature environmental protection. The type of foaming agent can be safely used in the process, and the by-products after decomposition will not cause harm to the living environment and the environment.

In order to achieve the above object, the present invention provides a chloroprene rubber foaming material, which comprises 100 parts by weight of sulfur-denatured chloroprene rubber, 50 to 60 parts by weight of a filler, 20 to 30 parts by weight of a reinforcing agent, 5 to 10 parts by weight of a softener, 20 to 29 parts by weight of a functional compounding agent, and 3.2 to 5.5 parts by weight of a vulcanizing agent, and specifically, the functional compounding agent contains 1 to 2 parts by weight of an antioxidant, 3 ～5 parts by weight of stearic acid, 1 to 2 parts by weight of polyethylene, and 15 to 20 parts by weight of a foaming agent, and the vulcanizing agent contains 3 to 5 parts by weight of zinc oxide and 0.2 to 0.5 parts by weight of ethylene thiourea ( ETU).

In more detail, the filler may be calcium carbonate, the reinforcing agent may be calcined earth, the softener may be a naphthenic processing oil, the antioxidant may be a coenzyme (Q-10), and the blowing agent may be two. Phenylsulfonyl ether (OBSH).

In addition, the present invention also provides a method for manufacturing a rubber composite layer, the steps of which are to provide a base fabric, and paste the surface of the base fabric to form a paste, and then provide a neoprene foaming material as described above, and then The neoprene foam material is kneaded into a rubber compound. Thereafter, the rubber compound is calendered into a rubber film, and then the rubber film is bonded to the paste to form a composite material. Finally, the composite material is placed in an open type. Sulfurization is carried out in a vulcanization apparatus to obtain a rubber composite layer.

According to the method for producing a neoprene foamed material and a rubber composite layer using the same according to the present invention, by using a sulfur-denatured neoprene in a formulation of a neoprene foamed material, sulfur molecules are allowed to be The grafting of the neoprene monomer, together with the vulcanizing agent specially used for the neoprene rubber, greatly shortens the scorch time. Therefore, it can be different from the production method of the mold used in the past batch production, can be vulcanized with the foaming agent without the mold pressure, and does not generate formaldehyde gas during foaming, and can simultaneously produce low-density continuous production of neoprene foaming material. And products.

Furthermore, in order to further improve the production safety, the invention can be used in the formulation of the neoprene foaming material in combination with the low-temperature environment-friendly foaming agent, as long as the foaming agent is added in the two-roller mixing step in the process, It is safe to use, and the by-products after decomposition will not cause harm to living things and the environment.

The purpose, technical content, features and effects achieved by the present invention will be more readily understood by the detailed description of the embodiments.

In order to clearly disclose the technical features of the method for producing a neoprene foamed material and a rubber composite layer using the same, a specific embodiment will be described below to explain the technical features of the present invention in detail, and more closely The schema makes these technical features stand out.

The invention provides a neoprene foaming material, which is mainly formulated by 100 parts by weight of sulfur-denatured neoprene rubber, 50-60 parts by weight of a filler, 20-30 parts by weight of a reinforcing agent, and 5-10 parts by weight. A softener, 20 to 29 parts by weight of a functional compounding agent, and 3.2 to 5.5 parts by weight of a vulcanizing agent. For example, the vulcanizing agent may comprise 3 to 5 parts by weight of zinc oxide and 0.2 to 0.5 parts by weight of ethylene thiourea (ETU); the functional complexing agent may comprise 1 to 2 parts by weight of antioxidant, 3 to 5 Parts by weight of stearic acid, 1 to 2 parts by weight of polyethylene and 15 to 20 parts by weight of a foaming agent; further, the filler may be calcium carbonate, the reinforcing agent may be calcined earth, and the softening agent may be Naphthenic processing oil, the antioxidant may be coenzyme (Q-10), and the blowing agent may be flaky diphenylsulfonyl oxime ether (OBSH).

It should be noted that, as used in the present specification, the amounts of various materials used are in units of "parts by weight", according to the contents of the present embodiment, wherein the neoprene foamed material contains a ratio of 100:50 to 60. : 20 to 30: 5 to 10: 20 to 29: 3.2 to 5.5 (parts by weight / part by weight / part by weight / part by weight / part by weight) of sulfur-denatured neoprene: filler: reinforcing agent: softening Agent: functional compounding agent: vulcanizing agent, that is, every 100 parts by weight of sulfur-denatured neoprene, the amount of filler used is 50-60 parts by weight, and the amount of reinforcing agent used is 20-30 parts by weight, softener The amount used is 5 to 10 parts by weight, the amount of the functional compounding agent is 20 to 29 parts by weight, and the amount of the vulcanizing agent used is 3.2 to 5.5 parts by weight, and if the parts by weight are converted into units of kilograms, it is equivalent. For every 100 kg of sulfur-denatured neoprene, the amount of filler used is 50-60 kg, the amount of reinforcing agent used is 20-30 kg, and the amount of softener used is 5-10 kg. Functional compounding agent The use amount is 20 ~ 29 kg, the use of vulcanizing agent 3.2 to 5.5 kg. The following description is also the case and will not be described again.

According to the chloroprene rubber foaming material disclosed in the present invention, the formulation does not generate formaldehyde during foaming, and at the same time, in order to make the chloroprene rubber having a slow vulcanization curve can be used for foaming and vulcanization in an open system, Sulfur-denatured neoprene, which allows sulfur molecules to be grafted in neoprene monomers, together with vulcanizing agents specifically for neoprene, such as zinc oxide (ZnO) and ethylene thiourea (ETU). The scorch time is drastically shortened, and the gas generated instantaneously by the blowing agent can be coated with the vulcanized colloid. Furthermore, in order to comply with environmental regulations, the foaming agent diphenylsulfonyl oxime ether (OBSH) may be used in combination with substances which are harmful to biological and environmental substances in the by-products after decomposition.

Next, please refer to FIG. 1 , which is a flow chart of a method for manufacturing a rubber composite layer using the above-mentioned neoprene foamed material according to an embodiment of the present invention. Meanwhile, please refer to FIG. 2A-2D , which is the present invention. A cross-sectional structural view corresponding to each step in the method for producing the rubber composite layer 10 to which the neoprene foamed material is applied is provided in the examples.

First, see step S01, as shown in FIG. 2A, a base fabric 20 is provided; wherein the base fabric 20 is made of nylon fiber cloth, and can also be replaced with polyester fiber cloth, cotton cloth, polyester/nylon blended gauze and other different compositions. Blended yarn weaving of fibers.

Referring to step S02, as shown in FIG. 2B, in order to maintain a stable flatness on the surface of the base fabric 20, the surface of the base fabric 20 is coated with a rubber paste by a coater (Coater), and dried by an oven. A surface resin layer 21 is formed on the surface of the base fabric 20 to form a paste cloth 22. Next, the rubber paste component comprises 250 parts by weight of toluene, 100 parts by weight of chloroprene rubber, 50 parts by weight of Bai Yanhua, 1 part by weight of an anti-aging agent, 1 part by weight of stearic acid, and 2 parts by weight of a release form. a component, 5 parts by weight of zinc oxide, and 1.5 parts by weight of a promoter; preferably, the old agent may be a coenzyme (Q-10), the release agent may be a polyethylene (PE), and the accelerator may comprise 1 weight. A portion of ethylene thiourea (ETU) and 0.5 parts by weight of dimethyldiphenyl thiuram disulfide (MPTD).

See step S03, providing the neoprene foamed material of the present invention as a raw material, as described above, the composition and composition ratio of the composition, including sulfur-modified neoprene, filler, reinforcing agent, softener, functional coordination And a vulcanizing agent; wherein the vulcanizing agent may comprise 3 to 5 parts by weight of zinc oxide and 0.2 to 0.5 parts by weight of ethylene thiourea (ETU); and the functional complexing agent may comprise 1 to 2 parts by weight of an antioxidant, 3 to 5 parts by weight of stearic acid, 1 to 2 parts by weight of polyethylene, and 15 to 20 parts by weight of a foaming agent; more specifically, sulfur-denatured chloroprene rubber may be selected from the sulphur-denatured type of Denka Corporation, PM-40NS Neoprene, and the filler may be calcium carbonate, the reinforcing agent may be calcined earth, the softener may be a naphthenic processing oil, the antioxidant may be a coenzyme (Q-10), and the foaming agent may be Flaky diphenylsulfonyl ether ether (OBSH).

Then, referring to step S04, the neoprene foamed material is kneaded into a rubber compound. In this embodiment, since a low-temperature foaming agent, i.e., diphenylsulfonyl oxime ether (OBSH), is used, it must be added during the mixing process to be added to the two-roller mixing step before entering the calendering stage. Therefore, the neoprene, softener, filler, reinforcing agent, antioxidant, stearic acid, and polyethylene were first kneaded in a 10,000-million kneading machine (Banbury) for 3 minutes; more specifically, the order of feeding was Functional ingredients (excluding antioxidants, stearic acid and polyethylene), fillers, reinforcing agents and softeners other than neoprene and foaming agents, the mixing temperature is controlled between 90 and 100 ° C, and it is cooled after mixing. The rubber box cools the rubber compound. Subsequently, the rubber compound obtained by the above kneading is added to the foaming agent and the vulcanizing agent, and fully mixed in a temperature range of 60 to 70 ° C with two rollers (including a coarse wheel and a fine wheel) for about 120 seconds. Rubber compound.

Next, in step S05, as shown in FIG. 2C, the rubber compound which is sufficiently mixed by the conveyor belt is sent to a continuous rubber calender (Calender), and the rubber compound must pass through the defoaming wheel to prevent the generation of wind smear. The rubber film 30 which has been subjected to thickness control and calendered to a set thickness has a thickness of about 0.28 to 0.30 cm (mm) and is attached to the surface resin layer 21 of the preheated base fabric 20, and the calender is a machine wheel The temperature is controlled at 60 to 70 ° C, and after calendering and laminating the rubber film 30, a rubber/fabric composite material is prepared, which can be continuously produced or coiled and prepared for the next process.

Finally, see step S06, as shown in Fig. 2D, the rubber/fabric composite prepared in step S05 is placed in an open vulcanization device, such as an upright hot air oven (Oven), for continuous vulcanization. The treatment has a vulcanization temperature of 140 to 150 ° C and a production rate of 15 to 18 yards per minute to achieve a sufficient amount of gas generation. Upon completion of the vulcanization, the rubber composite layer 10 is obtained.

The manufacturing method of the rubber composite layer using the neoprene foamed material disclosed in the embodiment of the present invention has an advantage in that it is different from the production method of the mold used in the past batch production, and the neoprene rubber provided by the present invention The foaming material can be vulcanized with a foaming agent without a mold pressure and at a vulcanization temperature of 140 to 150 ° C in an open system, and the scorch time can be greatly shortened, so that the gas generated by the foaming agent can be vulcanized. Covered with it, it can produce rubber products in a short time, suitable for batch and continuous process production. At the same time, due to the use of formaldehyde-free environmentally friendly formula, it can not only be safely used in the process, but also does not produce toxic in the process. By-products cause environmental pollution. The invention can be widely applied to the production of products with high softness and high durability, especially shoe materials or luggage materials.

In general, by using a neoprene foamed material disclosed in the present invention and a method for producing a rubber composite layer using the foamed material, sulfur-modified neoprene is used in the formulation of the neoprene foamed material. The sulfur molecules are grafted in the neoprene monomer, and together with the vulcanizing agent specially used for the neoprene rubber, the scorch time is greatly shortened. Therefore, the present invention has succeeded in overcoming the vulcanization characteristics of the neoprene rubber itself, allowing the neoprene foamed material to be vulcanized in an open system, and the rubber composite product can be produced in a short period of time, and the process is more efficient and can be greatly reduced. cost. At the same time, the formulation of the neoprene foaming material of the invention can meet the environmental protection standard, and does not generate formaldehyde gas during foaming, and if used together with the low-temperature environment-friendly foaming agent, as long as the foaming agent is in the process The roller mixing step is added to achieve safe use, and the environment does not produce environmentally hazardous substances, which can achieve the advantages of safety and non-toxicity, so it can replace the traditional neoprene foaming materials and products, and to a large extent Improves the functionality and characteristics of existing materials and processes.

The above is only the preferred embodiment of the present invention and is not intended to limit the scope of the present invention. Therefore, any changes or modifications of the features and spirits of the present invention should be included in the scope of the present invention.

10‧‧‧Rubber composite layer
20‧‧‧Kib
21‧‧‧Surface resin layer
22‧‧‧
30‧‧‧ Rubber film

Fig. 1 is a flow chart showing a method of manufacturing a rubber composite layer using a neoprene foamed material according to an embodiment of the present invention. 2A-2D is a cross-sectional structural view corresponding to each step in the method for producing a rubber composite layer using a neoprene foamed material according to an embodiment of the present invention.

Claims (8)

A neoprene foaming material, the formulation comprising: 100 parts by weight of sulfur-denatured neoprene; 50 to 60 parts by weight of a filler; 20 to 30 parts by weight of a reinforcing agent; and 5 to 10 parts by weight of a softening agent; 20 to 29 parts by weight of a functional compounding agent, the functional compounding agent comprising 1 to 2 parts by weight of an antioxidant, 3 to 5 parts by weight of stearic acid, 1 to 2 parts by weight of polyethylene, and 15 to 20 parts by weight a foaming agent; and 3.2 to 5.5 parts by weight of a vulcanizing agent, the vulcanizing agent comprising 3 to 5 parts by weight of zinc oxide and 0.2 to 0.5 parts by weight of ethylene thiourea (ETU); wherein the filler is calcium carbonate, The reinforcing agent is calcined earth, and the softening agent is a naphthenic processing oil, the antioxidant is coenzyme (Q-10), and the blowing agent is diphenylsulfonyl oxime ether (OBSH). A manufacturing method of a rubber composite layer comprising the steps of: providing a base fabric; pasting the surface of the base fabric to form a paste; and providing the neoprene foaming material according to claim 1 to the chlorine The rubber foaming material is kneaded into a rubber compound; the rubber rubber is calendered into a rubber film, and the rubber film is bonded to the cloth to form a composite material; and the composite material is placed in an open vulcanization device for vulcanization to obtain the rubber composite layer; wherein the kneading gelation step is first in the neoprene foaming material The chloroprene rubber, the softener, the filler, the reinforcing agent, the antioxidant, the stearic acid, and the polyethylene are kneaded in a temperature range of 90 to 100 ° C through a 10,000 horsepower kneading machine, and then added The foaming agent and the vulcanizing agent are uniformly mixed by two rollers in a temperature range of 60 to 70 ° C to form the rubber compound. The method for producing a rubber composite layer according to claim 2, wherein the base fabric is a nylon fiber cloth, a polyester fiber cloth, a cotton cloth, a polyester/nylon blended gauze, or a blended yarn woven fabric. The method for producing a rubber composite layer according to claim 2, wherein the step of smearing the base fabric is carried out by using a paste machine followed by a rubber paste. The method for producing a rubber composite layer according to Item 4, wherein the rubber paste comprises 250 parts by weight of toluene, 100 parts by weight of chloroprene rubber, 50 parts by weight of Bai Yanhua, and 1 part by weight of the old defense. A component, 1 part by weight of stearic acid, 2 parts by weight of a release agent, 5 parts by weight of zinc oxide, and 1.5 parts by weight of a promoter. The method for producing a rubber composite layer according to claim 5, wherein the old anti-agent is a coenzyme (Q-10), the release agent is polyethylene (PE), and the accelerator comprises 1 part by weight of ethylene sulfur. Urea (ETU) and 0.5 parts by weight of dimethyldiphenylthiuram disulfide (MPTD). The method for manufacturing a rubber composite layer according to Item 2, wherein the step of calendering is to feed the rubber compound into a continuous rubber calender to form and adhere to the paste, and calendering. The temperature is controlled at 60~70 °C, and the rolling thickness is controlled at 0.28~0.30 cm (mm). The method for manufacturing a rubber composite layer according to claim 2, wherein the open vulcanization device is a vertical hot air oven, and the vulcanization temperature of the vulcanization step is set to 140 to 150 ° C, and the production speed is set. It is 15~18 yards/minute.